JP2022119844A - Compatibilized polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compatibilized composition of a poly(para-phenylene sulfide)(PPS) and a poly(aryl ether sulfone) (PAES).

SOLUTION: A composition comprises i) a poly(para-phenylene sulfide) (PPS) and ii) a poly(aryl ether sulfone) (PAES) at a weight ratio of 0.2 to 20 to the PPS; and further comprises at least one alkali metal carbonate of 0.05 to 2 wt.% based on the total weight of polymers in the composition. At least part of the PAES is a reactive poly(aryl ether sulfone) (rPAES).

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62/329,522 filed April 29, 2016 and European Patent Application No. 16187800.4 filed September 8, 2016. and the entire contents of each of these applications are incorporated herein by reference for all purposes.

The present invention relates to high performance compatibilizing polymer compositions comprising poly(para-phenylene sulfide) (PPS) and at least one poly(aryl ether sulfone) (PAES).

Polymers may be blended to achieve new compositions with desired properties, however, most polymers are immiscible with each other. Attempts to blend polymers often result in heterogeneous multiphase compositions when the polymers are immiscible with each other. Such compositions exhibit several thermal transition temperatures (Tg, Tm), usually exhibit poor mechanical properties, and suffer from delamination and/or aesthetic defects.

In fact, the mechanical properties and ease of processing of a particular blend depend on the degree of compatibility of the polymer components. The major polymer component is commonly referred to as the continuous phase or matrix, while the minor polymer component is typically defined as the dispersed phase. The degree of compatibility can be characterized by the dimensions of the dispersed phase in the continuous phase and the level of adhesion between the matrix and the dispersed phase. Certain highly immiscible blends cannot be extruded under normal operating conditions due to high die swell and are therefore not commercially available.

PPS is known to have very good chemical resistance and low melt viscosity, and PAESs are known to have excellent mechanical properties and good thermal stability. Therefore, it is desirable to blend these polymers to achieve their combination of properties. However, the blends of PPS and PAES are not always very compatible, and in some cases the presence of large domains of individual polymers in blends of these polymers and poor adhesion between the phases. Therefore, it exhibits poor tensile properties.

Therefore, there is a need for new blends of PPS and PAESs with increased compatibility.

FIG. 1 shows transmission electron microscopy (TEM) images of the compositions of Example 1 (FIG. 1A) and Comparative Example 11 (FIG. 1B). Figure 2 shows TEM images of the compositions of Example 2 (Figure 2A) and Comparative Example 12 (Figure 2B). Figure 3 shows TEM images of the compositions of Example 3 (Figure 3) and Comparative Example 13 (Figure 3B). Figure 4 shows TEM images of the compositions of Example 4 (Figure 4A) and Comparative Example 14 (Figure 4B). Figure 5 shows TEM images of the compositions of Example 5 (Figure 5A) and Example 6 (Figure 5B). Figure 6 shows TEM images of the compositions of Example 7 (Figure 6A) and Example 8 (Figure 6B). Figure 7 shows TEM images of the compositions of Example 9 (Figure 7A) and Example 10 (Figure 7B). Figure 8 shows TEM images of the compositions of Example 15 (Figure 8A) and Comparative Example 18 (Figure 8B). Figure 9 shows TEM images of the compositions of Example 17 (Figure 8A) and Comparative Example 21 (Figure 8B). FIG. 10 shows a TEM image of the composition of Comparative Example 27. FIG. 11 shows a TEM image of the composition of Comparative Example 8. FIG. 12 shows a TEM image of the composition of Comparative Example 29. 13 shows a TEM image of the composition of Example 30. FIG.

Applicants have now surprisingly discovered increased phases, including blends of highly immiscible polymers such as poly(para-phenylene sulfide) (PPS) and poly(aryl ether sulfone) (PAES). We have discovered that it is possible to prepare soluble polymer blends.

An exemplary embodiment is a polymer composition comprising PPS, at least one PAES, and from about 0.05% to about 2% by weight of at least one alkali metal carbonate, based on the total weight of the polymer in the composition. about things. Preferably, the weight ratio of PPS to at least one PAES is in the range 0.2-20.

In some embodiments, the polymer composition is solvent-free or substantially solvent-free, i.e., the composition is solvent-free and contains 2% by weight (based on the total weight of the composition) of Solvent in an amount not exceeding, eg, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt%.

In some embodiments, the polymer composition is free or substantially free of polyetherimide (PEI), i.e., the composition is free of PEI and contains 2 wt. based on), for example, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt%.

In some embodiments, the polymer composition is free or substantially free of epoxy, i.e., the composition is epoxy-free and contains 2% by weight (based on the total weight of the composition) of Epoxy in an amount not exceeding, for example, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt%.

For clarity, throughout this application,
- the term "alkali metal carbonate" includes alkali metal carbonates and any reagent from which alkali metal carbonates can be derived in situ during processing at elevated temperatures, such as alkali metal hydrogencarbonates;
- the term "solvent" means a liquid in which at least one of the polymers in the polymer composition is at least partially dissolved;
- "substantially free of solvent" means less than 2% by weight, for example less than 1%, less than 0.5% or less than 0.1% by weight (based on the total weight of the composition) of solvent means;
- "substantially simultaneously" means within 30 seconds;
- "substantially free of polyetherimide (PEI)" means less than 2% by weight, such as less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight (based on the total weight of the composition) based on) polyetherimide (PEI);
- "substantially free of epoxy" means less than 2 wt%, such as less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt% (based on the total weight of the composition) of epoxy means;
- "substantially free of rPAES" means less than 2% by weight of rPAES, based on the total weight of the polymer in the polymer composition;
- "substantially free of die swell" means less than 5% die swell;
- The term "halogen" includes fluorine, chlorine, bromine and iodine unless otherwise specified.

Generally, PPS and PAES have weight average molecular weights ranging from 5,000 g/mol to 150,000 g/mol, preferably from 10,000 g/mol to 100,000 g/mol.

In this application:
- any description, even if described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the disclosure;
- in related embodiments expressly contemplated herein, when an element or component is said to be included in and/or selected from a recited list of elements or components, the element or component is It may also be any one of the individually recited elements or components, or may be selected from the group consisting of any two or more of the explicitly recited elements or components; any element or component listed in a list of may be omitted from such list; and - any recitation herein of numerical ranges by endpoints is included within the recited range. , as well as range endpoints and equivalents.

の繰り返し単位（Ｒ_ｐｐｓ）である、任意のポリマーを表す。 Poly(para-phenylene sulfide) (PPS)
As used herein, "poly(para-phenylene sulfide) (PPS)" means that at least 50 mol% of its repeating units are of the formula (L):

represents any polymer that is a repeating unit (R _pps ) of

Preferably, at least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, most preferably all of the repeating units in the PPS are repeating units (R _pps ).

PPS is manufactured and sold by Solvay Specialty Polymers USA, LLC under the trade name Ryton® PPS.

The PPS may or may not be acid washed. In some embodiments, the PPS is acetic acid washed PPS.

［式中：
（ｉ）それぞれのＲは、互いに等しいかまたは異なり、ハロゲン、アルキル、アルケニル、アルキニル、アリール、エーテル、チオエーテル、カルボン酸、エステル、アミド、イミド、アルカリまたはアルカリ土類金属スルホネート、アルキルスルホネート、アルカリまたはアルカリ土類金属ホスホネート、アルキルホスホネート、アミン、および第四級アンモニウムから選択され；
（ｉｉ）それぞれのｈは、互いに等しいかまたは異なり、０～４の範囲の整数であり；
（ｉｉｉ）Ｔは、結合、スルホン基［－Ｓ（＝Ｏ）_２］、および基－Ｃ（Ｒ_ｊ）（Ｒ_ｋ）－（ここで、Ｒ_ｊおよびＲ_ｋは、互いに等しいかまたは異なり、水素、ハロゲン、アルキル、アルケニル、アルキニル、エーテル、チオエーテル、カルボン酸、エステル、アミド、イミド、アルカリまたはアルカリ土類金属スルホネート、アルキルスルホネート、アルカリまたはアルカリ土類金属ホスホネート、アルキルホスホネート、アミン、および第四級アンモニウムから選択され、Ｒ_ｊおよびＲ_ｋは、好ましくはメチル基である）からなる群から選択される］
の繰り返し単位（Ｒ_ＰＡＥＳ）である任意のポリマーを表す。 Poly(aryl ether sulfone) (PAES)
For the purposes of the present invention, a "poly(arylethersulfone) (PAES)" is defined such that at least 50 mol% of its repeating units are of the formula (K):

[In the formula:
(i) each R is equal to or different from one another and is halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or selected from alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium;
(ii) each h is equal to or different from each other and is an integer ranging from 0 to 4;
(iii) T is a bond, a sulfone group [-S(=O) ₂ ], and a group -C(R _j )(R _k )-, where R _j and R _k are equal to or different from each other; hydrogen, halogens, alkyls, alkenyls, alkynyls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkylsulfonates, alkali or alkaline earth metal phosphonates, alkylphosphonates, amines, and quaternary ammonium and R _j and R _k are preferably methyl groups]
represents any polymer that is a repeating unit (R _PAES ) of

Preferably, at least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, most preferably all of the repeat units in the PAES are repeat units (R _PAES ).

の繰り返し単位である、任意のポリマーを表す。 In preferred embodiments, the PAES is polyphenylsulfone (PPSU). As used herein, "polyphenylsulfone (PPSU)" means that greater than 50 mol% of its repeating units are of the formula (K'-A):

represents any polymer that is a repeating unit of

Preferably, at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol%, most preferably all of the repeat units in the PPSU are repeats of formula (K'-A) Units.

PPSU can be prepared by known methods, particularly Solvay Specialty Polymers USA, L.L. L. C. available as RADEL® PPSU from .

の繰り返し単位である、任意のポリマーを表す。 In some embodiments, the PAES is polyethersulfone (PES). As used herein, "polyethersulfone (PES)" means that at least 50 mol% of its repeating units are of the formula (K'-B):

represents any polymer that is a repeating unit of

Preferably, at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol%, most preferably all of the repeat units in the PES are repeats of formula (K'-B) Units.

PES can be prepared by known methods, particularly Solvay Specialty Polymers USA, L.L. L. C. available as VERADEL® PESU from .

の繰り返し単位である、任意のポリマーを表す。 In some embodiments, the PAES is polysulfone (PSU). As used herein, "polysulfone (PSU)" means that at least 50 mol% of its repeating units are of the formula (K'-C):

represents any polymer that is a repeating unit of

Preferably, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, most preferably all of the repeating units in the PSU are represented by the formula (K' -C) is a repeating unit.

PSU can be prepared by known methods, particularly Solvay Specialty Polymers USA, L.L. L. C. available as the UDEL® PSU from .

Excellent results have been obtained when PAES is selected from the group consisting of PPSU, PES, PSU, or combinations thereof.

The alkali metal carbonate polymer composition contains about 0.05 to about 2 weight percent, about 0.1 to about 1.8 weight percent, about 0.1 to about 1.6 wt%, about 0.1 to about 1.5 wt%, about 0.1 to about 1.3 wt%, about 0.1 to about 1.0 wt%, about 0.1 to about 0.5 wt%. 8% by weight, comprising at least one alkali metal carbonate in an amount ranging from about 0.1 to about 0.5% by weight. In some embodiments, the amount of alkali metal carbonate is from about 0.1 to about 0.5 weight percent, from about 0.2 to about 0.5 weight percent, based on the total weight of the polymer in the polymer composition. %, in the range of about 0.4 to about 0.5 weight percent. In some embodiments, the amount of alkali metal carbonate, based on the total weight of the polymer in the polymer composition, is 1.0 wt% or less, 0.9 wt% or less, 0.8 wt% or less, 0 0.7% by weight or less, 0.6% by weight or less, 0.5% by weight or less, 0.4% by weight or less, 0.3% by weight or less, 0.2% by weight or less, or 0.1% by weight or less.

Alkali metal carbonates may be selected from sodium carbonate, potassium carbonate, cesium carbonate, and lithium carbonate. Potassium carbonate is preferred. Mixtures of two or more alkali metal carbonates may be used.

In some embodiments, the particle size D50 (median diameter or middle value of the particle size distribution) ranges from 2 microns to 1000 microns, preferably 2-500 microns, most preferably 3-200 microns.

Optional Reactive Polymers PPS and at least one PAES may exist in either reactive form (ie, reactive polymer) or non-reactive form.

In their reactive form, the polymers contain at least 5, at least 10, at least 15, preferably at least 20, preferably at least 50 microequivalents per gram (μeq/g) of hydroxyl (—OH) or thiol (—SH) terminated including groups. One example of such a reactive polymer is reactive polyethersulfone (rPES), available as VIRANTAGE® PESU from Solvay Specialty Polymers USA, LLC.

In some embodiments, the polymer composition comprises at least one reactive poly(arylethersulfone) (rPAES) in addition to PPS and at least one PAES. The rPAES is preferably selected from reactive polysulfone (rPSU), reactive polyethersulfone (rPES) and reactive polyphenylsulfone (rPPSU).

Preferably, the total amount of rPAES in the polymer composition is 0-60 wt%, 1-50 wt%, 5-30 wt%, 5-25 wt%, based on the total weight of the polymer in the polymer composition, It ranges from 5-20% by weight, 5-15% by weight, most preferably about 10% by weight.

In their non-reactive forms, PPS and PAES contain one or more non-reactive end groups. Non-reactive end groups are preferably -Cl, -F, or -O- _CH3 . Preferably, the non-reactive polymer contains at least 20, preferably more than 50 microequivalents per gram (μeq/g) of non-reactive end groups.

In some aspects, the polymer composition may be free or substantially free of rPAES.

PPS is preferably present in its reactive form. The abbreviation "PPS" as used herein includes both reactive and non-reactive poly(para-phenylene sulfide) (PPS).

Optional Reinforcing Fillers A wide selection of reinforcing fillers may be added to the polymer composition. They are preferably selected from fibrous and particulate fillers. A fibrous reinforcing filler is considered herein to be a material having a length, width and thickness whose average length is substantially greater than both the width and thickness. Preferably, such materials have an aspect ratio, defined as the average ratio between length and minimum width and thickness, of at least five. Preferably, the reinforcing fibers have an aspect ratio of at least 10, more preferably at least 20, even more preferably at least 50. The particulate filler has an aspect ratio of at most 5, preferably at most 2.

Preferably, the reinforcing filler is a mineral filler such as talc, mica, titanium dioxide, kaolin, calcium carbonate, calcium silicate, magnesium carbonate; glass fibres; carbon fibres, boron carbide fibres; wollastonite; Fiber; selected from boron fiber, graphene, carbon nanotube (CNT) and the like.

The reinforcing filler is present in the polymer composition in an amount of at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, based on the total weight of the polymer composition.

The reinforcing filler also preferably comprises at most 60 wt%, more preferably at most 50 wt%, even more preferably at most 40 wt%, based on the total weight of the polymer composition. present in quantity.

Preferably, the amount of reinforcing filler is in the range of 0.1% to 60%, more preferably 5% to 50%, even more preferably 10% to 40% by weight of the polymer composition. be. According to some embodiments, the polymer composition is free of fibrous fillers. Alternatively, the polymer composition may be free of particulate fillers. In certain embodiments, the polymer composition is preferably free of reinforcing fillers.

Additional Optional Ingredients In some embodiments, the polymer composition consists of or consists essentially of PPS, at least one PAES, and an alkali metal carbonate; however, in other embodiments, the polymer composition The article may contain one or more additional additives.

The polymer composition may contain other ingredients, such as colorants, such as dyes and/or pigments, such as titanium dioxide, zinc sulfide, zinc oxide, UV stabilizers, heat stabilizers, antioxidants, such as organic phosphorous. salts and phosphonites, acid scavengers, processing aids, nucleating agents, lubricants, flame retardants, smoke suppressants, antistatic agents, antiblocking agents, and/or conductive additives such as carbon black may further optionally include.

When one or more other ingredients are present, their total weight is preferably less than 20 wt%, less than 10 wt%, less than 5 wt%, most preferably less than 2 wt%, based on the total weight of the polymer composition. %.

Surprisingly, it has been discovered that organic and inorganic acid components with pKa<7.5, preferably pKa<7 can stabilize the melt viscosity of the polymer composition of the present invention. Non-limiting examples of organic and inorganic components with pKa<7.5 are sodium hydrogen phosphate _{( NaH2PO4} ), monosodium citrate, sodium hydrogen oxalate, and sodium hydrogen phthalate. Inorganic components with pKa< ₇ , such as _NaH2PO4 , are preferred. Excellent results have been obtained with organic and inorganic components having pKa's as follows: 2.5<pKa<7.5, preferably 3<pKa<7. The organic or inorganic acid component with a pKa <7.5 is from 0.05% to 5%, preferably from 0.1% to 2%, by weight, based on the total weight of the polymer in the polymer composition, and more It may preferably be present in an amount ranging from 0.2% to 1% by weight.

Exemplary Polymer Blends Preferred polymer compositions are shown in Table 1. Each polymer composition may contain other ingredients in addition to those listed. Each preferred polymer composition also contains an alkali metal carbonate, preferably potassium carbonate or sodium carbonate, in an amount ranging from 0.05 to about 2% by weight, or another amount as disclosed herein. include. Each preferred polymer composition may optionally include an acid component as described herein.

In the polymer composition, the concentration of each of PPS, PAES, and rPAES is 0 wt%, preferably at least 1 wt%, 2 wt%, 5 wt%, 10 wt%, of the total weight of the polymer in the polymer composition. 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt% %, 80%, 85%, 90%, 95%, 98%, 99% by weight.

In some embodiments, the polymer composition comprises about 85 wt%, preferably about 75 wt%, more preferably about 65 wt%, most preferably about 50 wt%, based on the total weight of the polymers in the polymer composition. % by weight of PPS or PAES and about 15% by weight, preferably about 25% by weight, more preferably about 35% by weight, most preferably about 50% by weight of the other of PPS or PAES, respectively.

In some aspects, the polymer composition comprises (i) 15 wt% to 85 wt%, preferably 25 to 75 wt%, 30 to 70 wt%, 40 wt%, based on the total weight of the polymer in the polymer composition. ~60 wt%, 45-55 wt%, most preferably about 45 wt% PPS, (ii) 85-15 wt%, preferably 75-25 wt%, 70-30 wt%, 60-40 wt%, 55-45 wt%, most preferably about 45 wt% PAES, and (iii) 1 wt% to 20 wt%, preferably about 10 wt% rPAES.

Preferably, the weight ratio of PPS to at least one PAES ranges from 0.2-20, 0.3-15, 0.4-10, 0.5-5, most preferably 1-3 .

In some embodiments, the weight ratio of PPS to the amount of at least one PAES ranges from 0.5 to 5, preferably from 1 to 3, and the polymer composition comprises Based on weight, it contains 0.15 to 0.4%, preferably 0.2 to 0.4% by weight of at least one alkali metal carbonate, preferably potassium carbonate or sodium carbonate.

In some embodiments, the polymer composition comprises
i) PPS;
ii) PPSU; and iii) from about 0.05% to about 2% by weight, based on the total weight of the polymer in the composition, of at least one alkali metal carbonate;
Here, the weight ratio of PPS/PPSU is in the range of 0.2-20.

Exemplary Properties of Polymer Compositions Polymer compositions of the present invention may comprise a continuous phase or a dispersed phase dispersed in a matrix. An example of a dispersed phase is shown in FIG. 4A.

In some embodiments, the average surface area per dispersed particle is preferably about 4 μm ² or less, about 3 μm ² or less, about 2 μm ² or less, about 1 μm ² or less, about 0.5 μm ² or less, about 0.25 μm ² or less. is.

In some embodiments, the largest diameter of the particles of the dispersed phase is ≤3 μm, preferably ≤2 μm, ≤1 μm, 0.8 μm, ≤0.6 μm, ≤0.4 μm, most preferably ≤0.1 ≤ μm. is.

In an alternative embodiment, the polymer blend may comprise a co-continuous phase characterized by the presence of continuous ribbons of polymer components when viewed by transmission electron microscopy (TEM). In such embodiments, the average width of the ribbons is preferably no greater than about 3 μm, more preferably no greater than about 2 μm, where the average width is taken from ten random measurements of ribbon width, the longest and shortest Calculated by discarding the measurement and dividing the sum of the remaining measurements by eight.

In some embodiments, the polymer compositions of the present invention exhibit a Dynatup Impact total energy according to ASTM D3763 in the range of 25-50 ft-lb.

The polymer composition may exhibit at least two different glass transition temperatures (Tg) corresponding to each of at least two different polymers; It may be different (ie, shifted) compared to the Tg of the same polymer. In some embodiments, the difference between each Tg (ΔTg) in the polymer composition is at least 0.5°C, preferably at least 1°C, more preferably 5-50°C, even more preferably 5-10°C. °C.

In certain embodiments, the polymer composition is free or substantially free of die swell when the polymer composition is extruded as a melt from the extruder, and the temperature of the melt is 300-430°C. is in the range of

Methods of Making Polymer Compositions In some embodiments, the present invention uses i) PPS, ii) at least one PAES, and iii) based on the total weight of the polymer in the composition, from about 0.05 to A method of making the polymer compositions described herein by melt mixing about 2% by weight of at least one alkali metal carbonate. Preferably, the weight ratio of PPS to at least one PAES is in the range 0.2-20, preferably 0.3-15, 0.4-10, 0.5-5, most preferably 1-3 is. Preferably, the polymer composition is free or substantially free of solvent. PPS and PAES may be independently reactive or non-reactive. PPS is preferably a reactive polymer. The PPS may or may not be acid washed.

The components of the mixture may be added or mixed in any order, in any amount or in any proportion of their total amount, and may be mixed separately or simultaneously.

Preparation of the polymer composition can be carried out by any known melt-mixing method suitable for preparing thermoplastic molding compositions. Such processes may be carried out by heating the polymer above the melting temperature of the semi-crystalline polymer and/or above the Tg of the amorphous polymer to form a melt of the polymer. In some embodiments, the processing temperature ranges from about 250-450°C, preferably 280-420°C. Preferably, the processing temperature is at least 15°C, preferably at least 50°C, preferably at least 100°C, preferably at least 150°C above the glass transition temperature (Tg) of the highest Tg polymer in the polymer composition, and/or At least 15°C higher than the melting temperature (Tm) of the highest Tm polymer in the polymer composition.

In some aspects of the process for preparing the polymer composition, the ingredients to form the polymer composition are fed to a melt mixing device and melt mixed in the device. Suitable melt-mixing devices are, for example, kneaders, Banbury mixers, single-screw extruders, twin-screw extruders. Preferably, an extruder is used that is fitted with means for charging the extruder with the desired components, either at the throat of the extruder or in the melt. Preferably, the extruder is equipped with one or more ports that allow the melt to be dosed at different barrels during the extrusion process.

The ingredients may be supplied together as a powder or granule mixture, also known as a dry blend, or may be supplied separately.

In some embodiments, the polymer and alkali metal carbonate are all added to the throat of the extruder, preferably at or substantially at the same time. In other embodiments, one or more of the polymers may be added to the extruder throat along with the alkali metal carbonate, and one or more other polymers are then added to the melt in the extruder barrel. be done. For example, PPS and rPAES, preferably rPES, may be added to the throat of the extruder along with the alkali metal carbonate, and PAES may then be added in the downstream barrel of the extruder. If added, the acid component may be added to the melt at the throat of the extruder or at either barrel of the extruder. Preferably, the acid component is added to the melt in the downstream barrel so that it contacts the melt just before it is extruded. Preferably, the acid component is added at a point after addition of the alkali metal carbonate.

In an exemplary embodiment, multiple pass extrusion may be performed. In multiple pass extrusion, the extrudate from the first pass is reintroduced into the extruder, preferably at the throat, so that it passes through the extruder once more. In multiple pass extrusion, 2, 3, 4, or more passes may be made, and the polymer, alkali metal carbonate, acid component, or other raw material may pass through the extruder line in any of the passes. It may be added at any point above. For example, PPS may be added to the throat of the extruder along with the alkali metal carbonate, and then the extrudate from the first pass may be recycled to the extruder with the addition of at least one PAES. Well, and the acid component can be added toward the end of the second pass. Alternatively, the extrudate obtained from the second pass may be recycled for a third pass, during which, for example, the acid component and/or filler material is melted prior to extrusion of the final product. may be added to the product.

In some embodiments, at least two passes may be performed, ingredients may be added to the extrudate, and/or the extrudate may be processed (e.g., mixed), followed by It is recycled to the extruder for one or more further passes.

The extruder may be operated at any suitable speed. The extruder speed and extruder barrel temperature may be constant or varied. Preferably, the extruder screws are rotated at about 100 to about 900, preferably about 200 to about 500 rpm; however, speed and temperature may be adjusted based on the particular polymer composition being blended. .

As used herein, "total residence time" means the total time spent in the extruder by the longest residence component, if any, including multiple passes, if any. Total residence time preferably ranges from about 15 seconds to 4 minutes, preferably from about 30 seconds to about 2 minutes.

The polymer compositions described herein are advantageously provided in the form of pellets, which may be used in injection molding or extrusion molding known in the art.

An exemplary embodiment is
(a1) contacting PPS, at least one PAES, and an alkali metal carbonate to form a first initial mixture;
(a2) contacting PPS with an alkali metal carbonate to form a second initial mixture, and then contacting the second initial mixture with at least one PAES to form a second mixture;
(a3) contacting at least one PAES with an alkali metal carbonate to form a third initial mixture, and then contacting the third initial mixture with PPS to form a third mixture; or (a4) contacting PPS with at least one PAES to form a fourth initial mixture, and then contacting the fourth initial mixture with an alkali metal carbonate to form a fourth mixture; and (b) optionally contacting the first initial mixture, the second mixture, the third mixture, or the fourth mixture with an acid component as described herein.

In an alternative embodiment, the method comprises:
(a1) contacting PPS, at least one PAES, rPAES and an alkali metal carbonate to form a first initial mixture;
(a2) contacting PPS, rPAES, and an alkali metal carbonate to form a second initial mixture, and then contacting the second initial mixture with at least one PAES to form a second mixture; the step of
(a3) contacting at least one PAES, rPAES, and an alkali metal carbonate to form a third initial mixture, and then contacting the third initial mixture with PPS to form a third mixture; or (a4) contacting PPS, at least one PAES, and rPAES to form a fourth initial mixture, and then contacting the fourth initial mixture with an alkali metal carbonate to form a fourth and (b) optionally the first initial mixture, the second mixture, the third mixture, or the fourth mixture with an acid component as described herein. A step of contacting is included.

In some embodiments, the method comprises:
(a1) contacting PPS, at least one PAES, and an alkali metal carbonate to form a first initial mixture, and then contacting the first initial mixture with rPAES to form a first mixture; the step of
(a2) contacting PPS and an alkali metal carbonate to form a second initial mixture, and then contacting the second initial mixture with at least one PAES, and rPAES to form a second mixture; the step of
(a3) contacting at least one PAES and an alkali metal carbonate to form a third initial mixture, and then contacting the third initial mixture with PPS and rPAES to form a third mixture; or (a4) contacting PPS and at least one PAES to form a fourth initial mixture, and then contacting the fourth initial mixture with an alkali metal carbonate and rPAES to form a fourth mixture. and (b) optionally contacting the first, second, third, or fourth mixture with an acid component as described herein. including.

Shaped Articles Comprising Polymer Compositions Exemplary embodiments also include articles comprising the polymer compositions described above.

Articles may be made from the polymer composition using any suitable melt processing method. In particular, they may be made by injection molding, extrusion, rotomolding or blow molding.

The polymer composition may be well suited for manufacturing articles useful in a wide variety of end uses.

The invention will now be illustrated in more detail in the following sections by non-limiting examples.

If the disclosure of any of the patents, patent applications, and publications incorporated herein by reference contradicts the description in this application to the extent that it may obscure terminology, the description shall control.

Examples 1 to 10 and Comparative Examples 11 to 14
Examples 1-10: Blends of PPSU and PPS with _K2CO3 Comparative Examples _11-14 : Blends of _PPSU and PPS without _K2CO3

material:
- Radel® PPSU R-5900 NT from Solvay Specialty Polymers USA, LLC
- Ryton® PPS QA200N from Solvay Specialty Polymers USA, LLC
- Ryton® PPS QA250N from Solvay Specialty Polymers USA, LLC
- Ryton® PPS QC160N from Solvay Specialty Polymers USA, LLC
- Ryton® PPS QC220N from Solvay Specialty Polymers USA, LLC
- _{K2CO3 ,} UNID EF-90

Compounding:
The blend was compounded using a Coperion® ZSK-26 co-rotating twin screw extruder with an L/D ratio of 48:1 at 200-300 rpm and 12-18 kg/hr. Barrel temperature set points were 360° C. for zones 1 through 6, 340° C. for zones 7 through 12, and 360° C. at the die.

measurement:
Melt viscosity was measured according to ASTM D5630 at 360° C. and 400 l/sec.

The morphology of the blends was investigated by transmission electron microscopy (TEM) to find the largest diameter of the dispersed phase domains.

result:
Blend compositions and measurements are shown in Table 2 below. The morphology of the blends is shown in the TEM images of Figures 1-7.

Comparing Example 1, Example 2, Example 3, and Example 4 with Comparative Example 11, Comparative Example 12, Comparative Example 13, and Comparative Example 14, respectively (see also FIGS. 1-4), unexpectedly Also _, the _addition of _{0.4 wt} . It has been found to significantly improve the compatibility of blends of PPSU and PPS, as evidenced by viscosity. A comparison of Examples 1 and 2 with Comparative Examples 11 and 12 shows that improved compatibility is achieved with PPSU-rich blends having PPSU as the continuous phase and PPS as the dispersed phase. , while comparing Examples 3 and 4 with Comparative Examples 13 and 14, improved compatibility is still achieved with PPS-rich blends having PPS as the continuous phase and PPSU as the dispersed phase. is shown.

Examples 5 through 10 (FIGS. 5-7) illustrate the effect of varying the PPS:PPSU ratio and the amount of K ₂ CO ₃ .

Examples 15 to 18 and Comparative Examples 19 to 22
Examples 15-18: Blends of PPSU, PPS, and _{K2CO3 ,} where the PPS was washed with acetic acid.

Comparative Examples 19-22: Blends of PPSU, PPS, and _{K2CO3 ,} where the PPS was not washed with acetic acid.

material:
- Radel® PPSU R-5900 NT from Solvay Specialty Polymers USA, LLC
- Ryton PPS QA250N from Solvay Specialty Polymers USA, LLC; acetic acid wash - Ryton PPS QC220N from Solvay Specialty Polymers USA, LLC; PPS PR34; water wash- _{K2CO3 ,} UNID EF-90

Compounding and Measurements Blends were compounded as in Example 1.

Melt viscosity and morphology measurements were performed as in Example 1.

result:
Blend compositions and measurements are shown in Table 3 below.

Comparing Example 15, Example 16, and Example 17 with Comparative Example 18, Comparative Example 19, Comparative Example 20, and Comparative Example 21 (see also FIGS. 8 and 9), the acetic acid washed PPS polymer unexpectedly improved the compatibility of blends of PPSU and PPS, as evidenced by the smaller dispersed phase domain size for blends using PPS polymer contacted with acetic acid. . In each case, the maximum dispersed phase domain size for blends using water- or calcium acetate-washed PPS polymers was surprisingly was bigger than

Examples 22 to 26
Comparative Example 22: PPS/PES Blends Examples 23-27: PPS/PES/K ₂ CO ₃ Blends The compositions are listed in Table 4.

material:
- Veradel® PESU 3300ULT from Solvay Specialty Polymers USA, LLC
- Ryton® PPS QA200N from Solvay Specialty Polymers USA, LLC
- Howard Industries, Inc.; K ₂ CO ₃ LH-90 from

Compounding:
The compositions in Table 4 were subjected to melt compounding using a 26 mm diameter Coperion® ZSK-26 co-rotating partially cross-rotating twin screw extruder with an L/D ratio of 48:1. Barrel sections 2 through 12 and the die were heated to set point temperatures as follows:
Barrels 2-6: 360°C
Barrel 7-12: 350°C
Die: 360°C

In each case, resins and additives were fed in barrel sections 1 and 5 using gravimetric feeders at throughput rates ranging from 30 to 40 pounds per hour. The extruder was operated at a screw speed of approximately 200 RPM. A vacuum was applied in barrel zone 10 with a vacuum level of about 27 inches of mercury. A single hole die was used for all compounds and the molten polymer strand exiting the die was cooled with a water trough and then cut with a pelletizer.

injection molding:
Injection molding was performed on the polymer composition to produce 3.2 mm (0.125 inch) thick ASTM tensile and flex specimens and 4 x 4 x 0.125 inch plaques for mechanical property testing. let me Type I tensile ASTM specimens and 4 x 4 x 0.125 inch plaques were injection molded using the following approximate temperature conditions in the barrel and mold:
Rear Zone: 680°F
Middle Zone: 680°F
Front Zone: 700°F
Nozzle: 700°F
Mold: 285°F

measurement:
Mechanical properties were determined on injection molded 0.125 inch thick ASTM specimens (4x4x0 on plaques) for the Dynatup impact test (D-3763: High Speed Puncture Multiaxial Impact). .125 inch) was used to test all formulations.

Chemical resistance (environmental stress cracking resistance) was evaluated by exposing the flexible bars to methyl ethyl ketone under variable stress for 24 hours. The time of exposure to methyl ethyl ketone was increased when the material showed no fractures or crazing.

result:
High speed drilling multiaxial impact (Dynatup Impact) data and tensile properties after heat aging are reported in Table 4:

The introduction of _{K2CO3 unexpectedly} enhanced the impact properties and environmental stress crack resistance of the PPS and PES blends.

Comparative Examples 27, 28 and 29, and Example 30
Comparative Example 27: Blend 50/50 parts PPS/PES for a 5 minute residence time.
Comparative Example 28: Blend PPS/PES/rPES 45/45/10 parts for a 5 minute residence time.
Comparative Example 29: Blend PPS/PES/rPES/ZnO 45/45/10/2 parts for a 3 minute residence time.
Example 30: Blend PPS/PES/rPES/ _K2CO3 45/45/10/0.5 parts for a ₃ minute residence time.

material:
- PPS Reference T4G from DIC Corporation
- Veradel® PESU 3600P from Solvay Specialty Polymers USA, LLC
- Reactive poly(ethersulfone) (rPES): rPES synthesized according to known processes from 4,4'-dichlorodiphenylsulfone, bisphenol S (in excess), potassium carbonate (in excess) in sulfolane as solvent. End-group titration of the rPES polymer gave:
○ Concentration of hydroxyl end groups [-OH] = 219 µeq/g
○ Concentration of potassium phenoxide terminal group [-OK] = 60 µeq/g
○ Concentration of chloro terminal group [-Cl] = 7 µeq/g
○ Number average molecular weight (Mn) = 2,000,000/([-OH] + [-OK] + [-Cl]) = 7,000 g/mole - Potassium carbonate K ₂ CO ₃ UNID EF-80
- zinc oxide ZnO

Compounding:
The blend was compounded on a DSM Xplore® twin-screw (100 rpm) extruder heated at 380° C. and equipped with a recirculation loop to allow control of residence time. The materials (7 g total) were introduced simultaneously, mixed for a period of time (residence time) and then extruded into strands.

measurement:
The torque required to rotate the extruder screw was measured during blending. Torque correlates with the viscosity of the melt blend, with higher forces indicating higher viscosities.

The level of die swell was observed at the exit of the extruder and ranked as follows: - very large die swell, - some die swell, + limited die swell, ++ no die swell.

Thermal properties, ie melting temperature and crystallization temperature, were determined by DSC.

The morphology of the blends was analyzed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to obtain the maximum diameter of the dispersed phase.

result:
Blend compositions and measurements are shown in Table 5 below. The morphology of the blends is shown in Figures 9-12.

PPS and PES are clearly immiscible as shown in FIG. As shown in Figure 11, the introduction of rPES (hydroxyl-terminated PES) did not significantly compatibilize the polymer and very large die swell was observed. Moreover, as shown in FIG. 12, further addition of base ZnO did not lead to dramatic changes in the morphology of the PPS and PES blends and some die swell was still observed.

Surprisingly, however, when another base _K2CO3 was added to the PPS, PES and _rPES polymer compositions, good phase Solubilization was observed. In addition, the polymer composition of Example 30 also unexpectedly exhibits no die swell, which is an advantage when extruding regular size strands, for example.

If the disclosure of any of the patents, patent applications, and publications incorporated herein by reference contradicts the description in this application to the extent that it may obscure terminology, the description shall control.

Examples 15 to 17 and Comparative Examples 18 to 21
Examples 15-17 : Blends of PPSU, PPS, and _{K2CO3 ,} where the PPS was washed with acetic acid.

Comparative Examples 18-21 : Blends of PPSU, PPS, and _{K2CO3 ,} where the PPS was not washed with acetic acid.

Claims (15)

A polymer composition comprising:
i) poly(para-phenylene sulfide) (PPS);
ii) at least one poly(aryl ether sulfone) (PAES); and iii) from about 0.05% to about 2% by weight, based on the total weight of polymers in said composition, of at least one alkali metal carbonate. including
The polymer composition, wherein the weight ratio of said poly(para-phenylene sulfide) (PPS) to said at least one poly(aryl ether sulfone) (PAES) is in the range of 0.2-20. 2. The polymer composition of claim 1, wherein the polymer composition is solvent-free or comprises a solvent in an amount not exceeding 2% by weight (based on the total weight of the composition). 3. The polymer composition of claim 1 or 2, wherein said poly(arylethersulfone) (PAES) is selected from the group consisting of polysulfone (PSU), polyethersulfone (PES) and polyphenylsulfone (PPSU). Polymer composition according to any one of the preceding claims, wherein said at least one alkali metal carbonate comprises sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, or combinations thereof, preferably potassium carbonate. thing. Claims 1-4, wherein the at least one alkali metal carbonate is potassium carbonate in an amount ranging from about 0.1 to about 0.5 weight percent based on the total weight of the polymer in the polymer composition. The polymer composition according to any one of Claims 1 to 3. - the weight ratio of said poly(para-phenylene sulfide) (PPS) to said at least one poly(aryl ether sulfone) (PAES) is in the range of 0.5 to 5, and - said polymer composition is , containing 0.15 to 0.4% by weight, based on the total weight of the polymer in said composition, of at least one alkali metal carbonate, preferably potassium carbonate;
A polymer composition according to any one of claims 1-5. Polymer composition according to any one of the preceding claims, wherein the poly(para-phenylene sulfide) (PPS) is acid washed poly(para-phenylene sulfide) (PPS). Polymer composition according to any one of the preceding claims, further comprising an acid component, preferably an inorganic acid component, more preferably NaH ₂ PO ₄ with a pKa ≤ 7.5. i) said at least one poly(arylethersulfone) (PAES) is a reactive poly(arylethersulfone) (rPAES); or ii) said polymer composition comprises at least one reactive poly( aryl ether sulfone) (rPAES), wherein said reactive poly(aryl ether sulfone) (rPAES) has —OH end groups at a concentration greater than 5 μeq/g of said reactive poly(aryl ether sulfone) (rPAES); The polymer composition of any one of claims 1-8, comprising: The polymer composition is
- a dispersed phase having a surface area of ≤ about ⁴ µm2 per dispersed particle,
or - a co-continuous phase in which the average width of a ribbon of a single polymer is about 2 μm or less, said average width being obtained by taking 10 random measurements of ribbon width, discarding the longest and shortest measurements, and Polymer composition according to any one of claims 1 to 9, comprising any of the co-continuous phases, calculated by dividing the sum of the measured values of by 8. The polymer composition is free or substantially free of polyetherimide (PEI) or free or substantially free of epoxy, preferably both polyetherimide (PEI) and epoxy The polymer composition according to any one of claims 1 to 10, which is free or substantially free of both. A method of making a polymer composition comprising:
i) poly(para-phenylene sulfide) (PPS);
ii) at least one poly(aryl ether sulfone) (PAES); and iii) from about 0.05% to about 2% by weight, based on the total weight of polymers in said composition, of at least one alkali metal carbonate. comprising a step of melting and mixing the
- the weight ratio of said poly(para-phenylene sulfide) (PPS) to said at least one poly(aryl ether sulfone) (PAES) is in the range of 0.2 to 20, and - said polymer composition is , substantially solvent-free, preferably solvent-free. (a1) contacting said poly(para-phenylene sulfide) (PPS), said at least one poly(aryl ether sulfone) (PAES), and said alkali metal carbonate to form a first initial mixture; ;
(a2) contacting said poly(para-phenylene sulfide) (PPS) with said alkali metal carbonate to form a second initial mixture; aryl ether sulfone) (PAES) to form a second mixture;
(a3) contacting said at least one poly(aryl ether sulfone) (PAES) with said alkali metal carbonate to form a third initial mixture; (a4) said poly(para-phenylene sulfide) (PPS) and said at least one poly(aryl ether sulfone (PAES); contacting to form a fourth initial mixture, and then contacting said fourth initial mixture with an alkali metal carbonate to form a fourth mixture; and (b) optionally, said fourth 13. The method of claim 12, comprising contacting an initial mixture of 1, said second mixture, said third mixture, or said fourth mixture with an acid component having a pKa<7,5. 14. A polymer composition made by the method of any one of claims 12 and 13. A shaped article comprising the polymer composition of any one of claims 1-11 and 14.

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